Bicyclo(n.1.0)alkyl ureas as herbicides

ABSTRACT

Bicyclo(n.1.0)alkyl-ureas of the formula   WHEREIN R1 represents hydrogen, a lower alkyl or alkoxy radical, R2 represents a lower alkyl, alkenyl or alkynyl radical, and N REPRESENTS AN INTEGER OF FROM 3 TO 6 ARE DISCLOSED AS HERBICIDALLY ACTIVE COMPOUNDS. Herbicidal compositions and a method of controlling undesirable plant growth with the aid of such compounds are also described.

United States Patent [1 1 Sturm et al.

1 1 Jan. 8, 1974 1 1 B1CYCLO(N.1.0)ALKYL UREAS AS HERBICIDES [73]Assignee: Ciba-Geigy C0r'p0ration,Ardsley,

[22] Filed: Aug. 31, 1972 [21] Appl. No.: 285,364

Related U.S. Application Data [62] Division of Ser. No. 886,356, Dec.18, 1969, Pat. No.

[52] U.S. CL, 71/119 [51] Int. Cl..... A0ln 9/20 [58.] Field of Search71/119; 260/453 R, 260/553 R [56] References Cited 1 UNITED STATESPATENTS 3,304,167 2/1967 Buntin et a1 260/563 P 3,454,393 7/1969 Mulleret a1. 71 /119 3,520,925 7/1970 Koenig et a1... 71/119 3,555,086 1/1971Weis et a1. 260/453 R 3,347,658 10/1967 Luckenbaugh 7l/l19 3,504,0303/1970 Vogt 260/563 P 3,527,756 9/1970 Szmuszkovics 26(1/563 P OTHERPUBLICATIONS Farbenfabriken Bayer, Prep. of Insecticides Miticides(1967), CA 67, no. 82282p. (1967) Primary Exam inerGlennon H. HollrahAttorneyKarl F. Jorda et a].

[57] ABSTRACT Bicyclo[n.1.0]a1kyl-ureasof the formula wherein Rrepresents hydrogen, a lower alkyl or alkoxy radical, R represents alower alkyl, alkenyl or alkynyl radical, and n represents an integer offrom 3 to 6 are disclosed as herbicidally active compounds. Herbicidalcompositions and a method of controlling undesirable plant growth withthe aid of such compounds are also described.

6 Claims, N0 Drawings ylureas of the Forrnel l2 7 1 BICYCLO(N.1.0)ALKYLUREAS AS HERBICIDES This is a division of application Ser. No. 886,356,filed Dec. 18, 1969 now US. Pat. No. 3,714,217.

DESCRIPTION OF THE INVENTION wherein R represents hydrogen, a loweralkyl or alkoxy radical,

R represents a lower alkyl, alkenyl or alkynyl radical, and t i nrepresents an integer of from 3 to 6, have a better herbicidal activitythan the known compounds mentioned above.

In the general Formula I, lower alkyl radicals R and R are straightchain or branched radicals having one to six, preferably one to fourcarbon atoms, e.g. methyl, ethyl, propyl, isopropyl, n-butyl, sec.butyl,tert.butyl, isobutyl. As lower alkenyl and alkynyl radicals can bementioned, e.g. the allyl, methallyl, a propenyl radical, the propynylor alkylpropynyl radical, allyl being preferred.

The novel bicyclo[n.l.Olalkyl-ureas of the Formula l are producedaccording to the present invention by reacting a bicyclo[n.l.0]alkylisocyanate of the Formula wherein R, and R, have themeanings givenabove.

The bicyclo[n.l.0]alkyl-ureas of the Formula I are of the Formula IVeither also obtained by reacting a bicyclo[n.l.0]alkyl-amine a. with acarbamt y l halide of the Formula V wherein Hal represents chlorine orbromine, or

b. with the components forming such a carbamoyl halide, namely phosgeneand an amine of the Formula III R, (III) c. with a chlorocarbonic acidderivative of the Formula VI c1--co-R wherein R represents chlorine orthe phenoxy radical to form a carbamic acid derivative and then reactingthis with an amine of Formula III, or

d. in those cases in which R represents hydrogen,

. with an isocyanate of the Formula VII,

RZNCO (VII) whereby in the Formulas II to V and VII the symbols R R andn have the meanings given for Formula I.

It is advisable to perform the reactionsa), b) and c) in the presence ofan acid-binding agent such as an organic base, e.g. a tertiary amine,etc., or an inorganic base, e.g. an alkali or alkaline earth metalhydroxide or oxide, or an alkali carbonate or hydrogen carbonate. Forthe reaction 0), preferable chlorocarbonic acid phenyl ester is employedas carbonic acid ester and the following carbamic acid ester is obtainedas intermediate product:

N-( bicycloln. I .0]aIkyIJ-O-phenyI-carbamate, and when phosgeneis used!N-(bicyclo[n.1,0]alkyl)-carbarnoyl chloride.

The reactions according to theinvention are usually performed in thepresence of solvents or diluentswhich are inert to the reactioncomponents. Suitable examples thereof are the following: aliphatic andaromatic hydrocarbons having from five to eight carbon atoms andhalohydrocarbons having one or two carbon atoms such as benzene,toluene, xylenes, chloroform, chlorinated ethylenes, N,N-dialkylatedamides such as dialkylformamides. Ether and ether-type compounds, suchas tetrahydrofurane and dioxane,high boiling ketones. such asmethylethylketone and diethylketone.

The novel ureas of Formula I, in which R, represents an alkoxy radicaland R represents a lower alkyl radical can also be produced bysubsequently alkylating an N-bicyclo[n.l.0]-alkyl-N'-hydroxy-urea withthe usual alkylating agents such as alkyl halides, dialkyl sulfates,etc. in the presence of an acid-binding agent. The N-bicyclo[n.l.O]alkyl-N'-hydroxy-ureas themselves can be obtained byreacting a bicyclo[n.l.0]alkylisocyanate with an N-alkyl-hydroxylamine.[0. Scherer, et

al., Angew. Chemie 75, 851-854 (1963)] The newbicyclo[n.l.0]alkyl-isocyanates (n 3, 5 or 6) serving as startingmaterialsare obtained according to the process of Curtius, by thermallydecomposing the azide of bicyclo[3.1.0]hexane-6-carboxylic acid,bicyclo[5.l.0]octane-8-carboxylic acid and of bicyclo-[6.1.0]nonane-9-corboxylic acid to the corresponding isocyanates.

The azides of the above-mentioned bicycloalkanecarboxylic acids areobtained by a) reacting the carboxylic acid chloride with an alkaliazide, b) reacting a lower alkyl ester with hydrazine and nitrous acid,or c) reacting the free acid with chloroformic acid-lower alkyl esterand alkali metal azide in the presence of a tertiary amine [J.Weinstock,.l. org. Chem. 26, 3511 1969)]. The reactions are preferably performedin the presence of a solvent or diluent. The azide is converted directlyinto the isocyanate by heating in a solvent, preferably in an aromatichydrocarbon.

Of the bicyclo[n.l.0]alkyl amines represented by Formula lV,bicyclo[3.l.0]hexyl(6)-amine, bicyclo[5.l .0]octyl (8)-amine andbicyclo[6.l.0]nonyl(9)- amine have not previously been described.Likewise the corresponding isocyanates falling under Formula ll,bicyclo[3.l.0]hexyl(6)-isocyanate, bicyclo[5.l.0]octyl( 8 )-isocyanateand bicyclo[6. l .0]nonyl(9)- isocyanate, are unknown.

The bicyclo[n.l.Olalkyl-amines of Formula [V used as starting materialare obtained by heating the corresponding isocyanates either a) with analkanol or b) with an acid. In the first case the carbamic acid ester(urethane) corresponding to the alkanol employed is obtained, which canbe converted to the amine by acid or alkaline hydrolysis. For thepreferred alkaline hydrolysis, inorganic bases, for example the alkaliand alkaline earth metal hydroxides and carbonates are especially wellsuited. The acid hydrolysis is performed with, halohydro-carbons,halogenated acetic acids or with mixtures of such acids. As solvents,water, alkanols having from one to three atoms and alkanol/watermixtures can be employed. ln case b), the amine salt is obtained whichcan be converted to the free base by neutralization.

Furthermore the amines of Formula IV may be prepared by the acidamide-rearrangement'according to Hofmann, comprising heating .acorresponding bicycloalkane-carboxylic acid amide in the presence of anagent giving off bromine or chlorine and in the presence of an alkali oralkaline earth metal hydroxide or an alkali metal alkanolate. For theacid amiderearrangement the following solvents can be employed: water,alkanols, especially lower alkanols, as well as alkanols correspondingto the optionally employed alkali metal alkanolate. When alkanols areemployed, a carbamic acid ester is obtained as intermediate productwhich can be' converted as described above into the amine.

The bicycloalkyl isocyanates of Formula ll, as well as thebicycloalkyl-amines of Formula IV can exist in two isomeric forms, asexoand as endo-isomers.

. The novel ureas of Formula I possess excellent herbicidal properties.Since the herbicidal activity is inherent in the ureas obtained fromboth the exoand the endo-isomeric amines and isocyanates, the expressionureas of the Formula I includes the exo-, endoand mixtures of bothisomeric bicyclo[n.l.0]-alkyl-ureas.

They can be employed for the control of monoand dicotyledoneous weedsand wild grasses. In concentrations, between 0.2 and 8 kg/ha, the newureas have a selective herbicidal effect. The action of these substancesincludes the types of weeds which are difficult to control as well asthe deep rooted types, e.g. leguminous and umbelliferous plants. Theycan be applied with equal success before (preemergence) and afteremergence (postemergence) of the plants. Thus field weeds, such as typesof millet (Panicum sp.), types of mustard (Sinapis sp.), types of goosefoot (Chenopodiaceae), field foxtail (Alopecurus sp.),

types of chamomile (matricaria sp-),can be destroyed or their growth canbe hindered without damaging cultivated plants such as grains, etc.

For the preparation of herbicidal agents, the active substances aremixed with suitable carriers and/or dispersing agents. To widen therange of action, these agents can be admixed with other herbicides, forexample triazines such as halogen-diamino-s-triazines, alkoxyandalkylthio-diamino s-triazines, triazoles, diazines such as uracils,aliphatic carboxylic acids and halogen carboxylic acids, halogenatedbenzoic acids and phenylacetic acids, aryloxyalkane carboxylic acids,hydrazides, amides, nitriles, esters of such carboxylic acids, carbamicacid esters and thiocarbamic acid esters, ureas, etc.

Representatives of such herbicidally active sub stances which can beadmixed are, e.g., the following compounds:

2-chloro-4,6-bis(ethylamino)-s-triazine,

2-chloro-4-ethylamino-6-isopropylamino-s-triazine,

2-chloro-4,6-bis-(methoxypropylamino)-s-triazine,2-methoxy-4,6-bis-(isopropylamino)-s-triazine,2-diethylamino-4-isopropylacetamido-6-methoxy-striazine,2-isopropylamino-4-methoxypropylamino-6-methylthio-s-triazine,2-methylthio-4,6-bis-(isopropylamino)-s-triazine,2-methylthio-4,6-bis-(ethylamino)-s-triazine,

Z-methylthio-4-ethylamino-6-isopropylamino-striazine,2-methoxy-4-ethylamino-6-isopropylamino-striazine,2-methoxy-4,6-bis-(ethylamino)-s-triazine,2-chloro-4,6-bis-(isopropylamino)-s-triazine,5-bromo-3-sec-butyl-o-methyl-uracil,

S-amino-S-chloro-l-phenyl-pyridazone-(6),

3 ,6-dioxol ,2,3 ,6-tetrahydropyridazine,

dinitro-sec-butylphenol and salts thereof,

pentachlorophenol and salts thereof, trichloroacetic acid and saltsthereof, 2,2-dichloropropionic acid and salts thereof,2-chloro-N,N-diallylacetic. acid amide,

maleic acid hydrazide,

2,3,6-trichlorobenzoic acid and salts thereof,

2,3,5,6-tetrachlorobenzoic acid and salts thereof,2-methoxy-3,5,6-trichlorobenzoic acid and salts thereof,2-methoxy-3,6-dichlorobenzoic thereof, 3-amino-2,S-dichlorobenzoic acidand salts thereof 3-nitr0-2,5-dichlorobenzoic acid and salts thereof,2-methyl-3,-dichlorobenzoic acid and salts thereof,2,6-dichloro-benzonitrile, 2,6-dichloro-thiobenzamide,2,3,o-trichlorophenylacetic acid and salts thereof,

acid and salts 2,4-dichlorophenoxyacetic acid and salts thereof,

2,4,5-trichlorophenoxyacetic acid, and salts and esters thereof, I

(2-methyl4-chlorophenoxy)-acetic acid, and salts and esters thereof, I

2-(2,4,5-trichlorophenoxy)-propionic acid, and salts and esters thereof,

'2-(2,4,5-trichlorophenoxy)-ethyl-2,2-

dichloropropionate, 4-(2,4-dichlorophenoxy)-butyric acid, and salts andesters thereof, 4-(2-methyl-4-chlorophenoxy)-butyric salts and estersthereof, 2,3,6-trichlorobenzyloxypropanol,4-amino-3,5,fi-trichloropicolinic acid,

N-cyclooctyl-N,N-dimethyl-urea,

3-phenyl-1,l-dimethyl-urea,-

3-(4'-chlorophenyl)-l 1 -dimethyl-urea,

3-( 3 '-trifluoromethylphenyl)- l l -'dimethyl-urea,

3-( 3 ,4'-dichlorophenyl)-1,l-dimethyl-urea,

3 3 ',4'-dichlorophenyl)- l '-n-butyll methyl-urea,

3-( 3 ',4'-dichlorophenyl )-l l ,3-trimethyhurea,

3-( 3 ',4'-dichlorophenyl)-l l diethyl-urea,

3-(4'-chlorophenyl)-l-methoxy-l-methyl-urea,

3-(3.,4'-dichlorophenyl)-l-rnethoxy+l-methyl-urea,3-(4'-bromophenyl)-l-methoxyl-methyl-urea,

3-( 3 ,4-dichlorophenyl)-3-methoxyl l -dimethylurea,

3-( 4'-chlorophenoxyphenyl)-l l -dimethyl-urea,

N,N-di-(propyl)-S-ethyl-thiocarbamate,

N,N-di-(n-propyl)-S-n-propyl-thiocarbamate,

N-ethyl-N-(n-butyl)-S-n-propyl-thiocarbamate,

N-phenyl--isopropyl-carbamate,

N-(m-chlorophenyl)-0isopropyl-carbamate,

N-(m-chlorophenyl)-0-4chloro-butyn-(2)-ylcarbamate,

N-(3',4'-dichlorophenyl)-0-methyl-carbamate.

The following examples illustrate the process for the production of thenew compounds of Formula I. Where not stated otherweise, temperaturesare expressed in degrees centigrade.

acid, and

EXAMPLE 1 Dimethylamine is introduced at 0-l0 into a solution of 240 gof bicyclo[6.l.0]nonyl(9)-exo-isocyanate in 1,000 ml of anhydroustoluene until excess gas can be detected.

After 1 hour the solvent is distilled off in vacuo and the residue isrecrystallised from hexane/benzene. 230 g of colourlessNbicylo[6.l.0]nonyl(9)-N,N'- dimethyl-urea having a melting point ofl36l38 are obtained.

The bicyclo[6.1.0]nonyl(9)-exo-isocyanate used as starting material isproduced as follows:

Twenty g of bicyclo[6.l.0]nonane-9-carboxylic acid ethyl ester [of S.Akiyoshi and T. Matsuda, J. Amer. Chem. Soc. 77, 2476 (1955)] are addeddropwise with stirring and at 100 to a mixture of. 13 g of 98 percent byweight hydrazin hydrate and 2 ml of dioxane. After the addition of theester, the mixture is refluxed for 8 hours and then cooled. 100 ml ofpetroleum ether are added to the crystalline slurrey obtained and, afterstirring, the solvent is removed by suction. The hydrazide is washedwith ice water until it is neutral and dried in vacuo. The resultantbicyclo[6.l.0]nonane-9- carboxylic acid hydrazide, recrystallised fromhexane/- toluene has a melting point of l76-l77.

32 g of bicyclo[6.l.0]nonane-9-carboxylic acid hydrazide are dissolvedat 5 to +5 in a solution of 25 g of concentrated hydrochloric acid and350 ml of water. This solution is added dropwise with vigorous stirringto a mixture of 28 g of concentrated hydrochloric acid and 250 ml oftoluene. A solution of 15 g of sodium nitrite in 50 ml of water issimultaneously added dropwise to the mixture. The reaction mixture isthen stirred for 30 minutes at 0. The layers formed are sepa rated andthe aqueous phase is again extracted with 100 ml of toluene. The toluenesolutions are combined and washed with a sodium bicarbonate solution andthen dried at 0 over sodium sulfate. The carboxylic acid azide solutionis heated carefully at to until the strong nitrogen formation hassubsided. The solution is refluxed for another 30 minutes and thetoluene is removed by distillation. The residue is fractionated invacuo. The bicyclo[6.l.0]nonyl(9)-exo-isocyanate boils at 1l6-120 and 13Torr.

According to the above method, on using the corre spondingbicyclo[n.1.0]alkyl-carboxylic acid esters, the following isocyanat esof Formula II can be obtained:

bicyclo[3.l.0]hexyl (6) exoisocyanate bicyclol4. l .Olheptyl (7)-exo-isocyanate bicyclo[5.l.0]octyl (8) -exo-isocyanate V b.p. 92-95/l 2Torr EXAMPLE '2 EXAMPLE 3 Forty g of bicyclo[5.l.0]octyl(8)'exo-amineand l g of triethylamine are dissolved in'50'0 ml of benzene and addeddropwise at 0-5 to 18,5 gof methyl isocyanate. Then the reaction mixtureis stirred for 2 more hours at 25; all of the volatile components arethen removed in vacuum. The residue is crystalline. The N-bicyclo[5.l.0]octyl(8)N'-methyl-urea, recrystallized frombenzene/hexane, has a melting point of 108-ll0. t

The bicyclo[5.l.0]octyl(8)-exo-amine used as starting compound isprepared as follows:

17,5 g of bicyclo[5.l.0]octyl(8)-exo-isocyanate are dissolved in ml ofbenzene, and 60 ml of concentrated hydrochloric acid are added, and themixture is refluxed for 2 hours until the generation of CO has subsided.The benzene is removed by distillation in vacuum and the brown residueis made strongly alkaline with concentrated sodium hydroxide solution,the free amine precipitating as a brown oil.

The bicyclo[5.l.0]octyl(8)-exo-amine is distilled in vacuum and boils at75-78/-l5 mm as a colorless oil.

According to this method the following amines may be produced: t

exo-amine b.p. 86-88/l l Torr EXAMPLE 4 Thirty-five g ofdimethyl-carbamoyl chloride dissolved in 100 ml of benzene are addeddropwise at 5l0 to a solution of 40 g of bicyclo[5.l.0]octyl(8)-exo-amine and 33 g of triethylamine in 500 ml of benzene. After stirringfor 3 hours at 25, the precipitated triethylamine hydrochloride isremoved by filtration. The benzene solution is washed with water, driedand the benzene is evaporated in vacuum. The crystalline N-bicyclo-[ 5.l .O]octyl( 8 )-N',N'dimethyl-urea obtained, recrystallized frombenzenelhexane, has a melting point of ll02.

EXAMPLE Fifty g of bicyclo[4.l.0]heptyl(7)-carbamoyl chloride, whichhave been suspended in 500 ml of petroleum ether, are treated with anexcess of dry methylamine at 05. After stirring for 2 hours at roomtemperature, the petroleum ether is removed and the residue is suspendedin water. The N-bicyclo[4.l.0]-heptyl(7)-N'- methyl-urea is removed bysuction, and dried. Recrystallized from hexane/benzene, it has a meltingpoint of l45-l46.

The bicyclo[4.l.0]heptyl(7)-carbamoyl chloride used as starting materialis produced as follows: 40 parts of bicyclo[4.l.O]heptyl(7)-amine[.I.Org.- Chem 28, 3356 (1963)] are dissolved in 500 parts by volume ofpetroleum ether and this solution is saturated with phosgene at 0. TheN-bicyclo[4.l.0]heptyl(7)-carbamoyl chloride separates as a whiteprecipitate and has a melting point of 4l45. The suspension of thebicyclo[4.1.0]heptyl(7) carbamoyl chloride in petroleum ether is useddirectly in the above-described reaction.

EXAMPLE 6 An aqueous solution of 2,0 g of N-methylhydroxylamine is addeddropwise while stirring and cooling to a solution of 7,0gbicyclo[6.l.0]nonyl(9)-isocyanate in 50 ml of anhydrous diethyl ether.After 1 hour the organic layer is separated, the aqueous layer isextracted again with 50 ml of diethyl ether and the diethyl ether isevaporated in vacuo. The solid crystalline residue obtained isrecrystallised from hexane. N-bicyclo[6.l.0]-nonyl(9)-N'-hydroxy-N-methyl-urea is obtained, having a melting point of93*94.

To a solution of 4,3 g of N-bicyclo[6.1.0]nonyl(9)- N'-hydroxy-N'-methylurea in 50 ml of methanol, there is added while cooling, first asolution of 0,9 g of sodium hydroxide in 50 ml of methanol and then 3,4g of diethyl sulfate. The reaction mixture is stirred for 8 hours atroom temperature (23). The major part of the methanol is evaporated invacuo and ice Water is added. The separated oil is extracted withmethylene chloride. The solvent is evaporated and a viscous oil isobtained, which soon crystallises. On recrystallisation from hexane, 3,2g of N-bicyclo[6.l.0]nonyl(9)-N'- ethoxy-N'-methyl urea, having amelting point of 67-68, are obtained.

The following urea derivatives of the general Formula l were producedanalogously to the preceding examples:

TABLE l Compounds: Melting The herbicidal activity of the new compoundsof the Formula I is shown by the following tests:

1. Preemergence test The active substance was mixed in the form of a 10percent by weight powder concentrate to garden soil to obtain aconcentration of 100 mg (milligram) per 1,000 ml of soil. The followingtest plants were sown in seed dishes containing the prepared soil: oats,mustard, ray grass, barley, tomatoes and vetch.

The dishes were then kept in a greenhouse at 2024C and at percentrelative humidity and continuously illuminated. The tests were evaluatedafter 20 days according to the following scale:

10 no damage control plant) 9-1 increasing degrees of damage 0 plantsdestroyed The following compounds have been tested:

TABLE II NR./Compound l N-bicyclo[ 3. 1 .0]hexyl( 6)-N-methyl-urea 2N-bicyclo[ 3. l .0]hexyl( 6')-'N',N'-dimethyl-urea 3 t 10 mixing 25parts of active substance, 32,5 parts of isophorone, 32,5 parts ofmethylethyl ketone and 10 parts of an emulsifier consisting ofnonylphenol- 16 N-b1cyclo[5.l.0]octyl(8)-N-alkyl-urea polyoxyethyleneand dodecylbenzene-calc1um sulfo- 17 5 nate.

TABLE III Preemergence Postemergenoe Compound number Rye (Table II) Oatsgrass Mustard Tomatoes Veteh Barley Oats Mustard '0 O 0 0 0 0 0 4 2 5 60 0 3 O 0 0 5 1 0 1 0 1 0 3 2 0 0 4 3 1 1 0 O 0 0 0 0 3 1 *Not tested.

l8 N-bicyclo[6.1.0]nonyl(9)-N'-methyl-urea l9N-bicyclo[6.1.0]nonyl(9)-N,N'-dimethyl-urea The 10 percent by weightpowder concentrate used had the following composition: 10 parts ofactive substance, 0,6 part of dibutylnaphthalene sodiumsulfonate, 1 partof naphthalene sulfonic acids/phenol sulfonic acids/formaldehydecondensate (ratio 3:221), l0'parts of sodium-aluminium silicate and 78,4parts of kaolin. 2. Postemergenc e test (A) 3. Postemergence test (B)The following were sown in seed traysas test plants:

rye grass (Laliuim mulujiorum) chamomile (Matricaria chamom illa) barley(Panicum ilalicum) dandelion (Taraxacum offlcinalir) vetch (Vicia:saliva) and ffoxlail (Amaranlhus descendenr) in the four-leaf stage,theplants are treated with a 2 TABLE IV Weeds Compound Concennumbertratiori, Rye Chamo- Dande- (Table II) kgJho grass mile Barley lionVetoh Foxtail;

0.5 7 a 4 1 a 1 5:2 2 .2 t a a a 8N-bieyclo[3.3.0]oetyi-N,NWimethyi-urea known from the German patentapplication open for public inspection No. 1221841.

Oats and mustard plants in the fourto six-leaf stage were sprayed withan aqueous emulsion of the active substance in a concentration of 0,5 gof active substance per square meter ofsoil. The emulsion was obtainedfrom a 25 percent by weight emulsifiable concentrate. The plants werethen kept at 2528C and 40 to percent relative humidity. The tests wereevaluated 14 days after treatment according to the following scale: 1

10 no damage control plant) 9-1 increasing degrees of damage 0 plantsdestroyed Theemulsifiable concentrate used was preparedby .4.Preemergenee test with sown test plants Immediately after the testplants have been sown, the active substances are applied tothe surfaceof the soil as an aqueous suspension obtained from a 25 percent wettablepowder. The seed trays are then kept under continuous illumination at22-23 and 5070 percent relative humidity.

The following test plants were sown:

,ltalian rye grass (Lolium mulnflarum) barley (Seraria italics, Panicumimlr'cum) mustard (Sinapir alba) 59.!91. (Gosrypium herbnccara) 1 l Thetest plant s were evaluat edafteriirdafiaccording to the followingscale:

9 plants undamaged control) 1 plants dead 8-2 intermediate degrees ofdamage TABLE V Cultivated Weeds plants Compound Concennumber tration, RyMus- (Table II) kgJha. grass Barley tard Wheat Cotton 0. 5 3 4 9 19 2 12 8 9 2 4 3 3 8 9 Comparison 1 9 8 6 9 9 0.5 9 9 9 9 9N-bicyelofii.3.0]oetyl-N,N-dimethyl-urea known from the German patentapplication open for public inspection No. 1221841. I

l The productionof herbicidal compositions according to the invention isperformed in known manner by inti mate mixing and grinding of activesubstances of the general Formula l together with suitable carriers,optionally with the addition of dispersing agents or solvents, which areinert towards the active substances. The active substances can be usedand applied, e.g. as:

dusts, scattering agents, granulates, coated granulates, impregnatedgranulates, homogeneous granulates, wettable powders, pastes, emulsionsor solutions.

For the production of solid preparations (dusts, scattering agents,granulates) the active ingredients are mixed with solid carriers.Examples of suitable carriers are kaolin, talcum, bole, loess, chalk,limestone, ground limestone, attaclay, dolomite, diatomaceous earth,precipitated silicic acid, alkaline earth silicates,

sodium and potassium aluminium silicates (feldspar and mica), calciumand magnesium sulfates, magnesium oxide, ground synthetic plastics,fertilizers such as ammonium sulfate, ammonium phosphates, ammoniumnitrate, urea, ground vegetable products such as,

about 0,075 to 0,2 mm and for granulates 0,2 mm or coarser.

The concentrations of activesubstance in the solid preparations are from0,5 to percent.

To these mixtures can also be added additives which stabilize the activesubstance and/or non-ionic, anionic and cationic surface activesubstances, which for example, improve the adhesion of the activeingredients on plants or parts of plants (adhesives and agglutinants)and/or ensure a better wettability (wetting agents) and dispersibility(dispersing agents). Examples of suitable adhesives are the following:olein/chalk mixture, cellulose derivatives (methyl cellulose,carboxymethyl cellulose), hydroxyethyl glycol ethers of monoalkyl anddialkyl phenols having 5-l 5 ethylene oxide radicals per molecule andeight to nine carbon atoms in the alkyl radical, lignin sulfonic acids,theiralkali metal and alkaline earth metal salts, polyethylene glycolethers (carbowaxes), fatty alcohol polyethylene glycol ethers havingfive to 20 ethylene oxide radicals per molecule and eight to 18 carbonatoms in the fatty alcohol moiety, condensation products of ethyleneoxide, propylene oxide, polyvinyl pyrrolidones, polyvinyl alcohols,condensation products of urea and formaldehyde, and also latex products.

The water-dispersible concentrates of the active substance, i.e.wettable powders, pastes and emulsion concentrates, are compositionswhich can be diluted with water to any concentration desired. Theyconsist of active substance, carrier, optionally additives whichstabilize the active substance, surface-active substances and anti-foamagents and, optionally, solvents. The concentration of active substancein these agents is 580 percent.

Wettable powders and pastes are obtained by mixing and grinding theactive substances with dispersing agents and pulverulent carriers insuitable apparatus until homogeneity is attained. Carriers are, forexample, those mentioned for the solid forms of application. In somecases it is advantageous to use mixtures of different carriers. Asdispersing agents there can be used, for example, condensation productsof sulfonated naphthalene and sulfonated naphthalene derivatives withformaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, as well as alkali, ammoniumand alkaline earth metal salts of lignin sulfonic acid, in addition,alkylaryl sulfonates, alkali and alkaline earth metal salts of dibutylnaphthalene sulfonic acid, fatty alcohol sulfates such as salts ofsulfated hexadecanols, heptadecanols, octadecanols, and salts ofsulfated fatty alcohol glycol ethers, the sodium salt of oleoylethionate, the sodium salt of oleoyl methyl tauride, ditertiaryacetylene glycols, dialkyl dilauryl ammonium chloride and fatty acidalkali and alkaline earth metal salts.

Suitable anti-foam agents are, for example, silicones.

The active substances are somixed, ground, sieved and strained with theadditives mentioned above that,

in wettable powders, the solid particle size of from 0,02

to 0,04 and in pastes, of 0,03 is not exceeded. To produce emulsionconcentrates andpastes, dispersing agents such as those given in theprevious paragraphs, organic solvents and water are used. Examples ofsuitable solvents are the following: alcohols, benzene, xylenes,toluene, dimethyl sulfoxide, and mineral oil fractions boiling between120 and 350. The solvents must be practically odorless, notphytotoxic,inert to the active substances and not readily inflammable.

Furthermore, the compositions according to the invention can be appliedin theform of solutions. For this purpose the active substance orseveral active substances of general Formula I are dissolved in suitableorganic solvents, mixtures of solvents or in water. Aliphatic andaromatic hydrocarbons, chlorinated derivatives thereof, alkylnaphthalenes and mineral oils alone or mixed with each other can be usedas organic solvents. The solution should contain the active substancesin a concentration of from 1 to 20 percent.

The compositions described according to the invention can be mixed withother biocidally active compounds or agents. Thus to broaden the rangeof action, the new compositions can contain, e.g. insecticides,fungicides, bactericides, fungistatics, bacteriostatics or nematocidesin addition to the compounds mentioned of the general Formula I. Thecompositions according to the invention can also contain fertilizers,trace elements, etc.

in the following, application forms of the new ureas are described.Parts mean parts by weight.

EXAMPLE 7 The following ingredients are used to produce a 5 granulate:

5 parts of N-bicyclo[5.l.0]octyl(8)-N-methyl-urea,

0,25 part of epichlorohydrin,

0,25 part of cetyl polyglycol ether with 8 mol ethyleneoxide 3,50 partsof polyglycol (carbowax),

91 parts of kaolin (particle size 0,3-0,8 mm).

The active ingredient is mixed with epichlorohydrin and dissolved in 6parts of acetone, then the polyglycol and cetyl polyglycol ether areadded. The resulting so lution is sprayed onto kaolin and thenevaporated in vacuum.

EXAMPLE'8 The following components are used for the preparation of a) 50percent, b) 25 percent and c) percent wettable powders:

a. 50 parts of N-bicyclo[5.l.0]octyl(8)-N',N'-

dimethylurea,

5 parts of sodium dibutylnaphthyl sulfonate,

3 parts of naphthalene sulfonic acid/phenol sulfonic acid/formaldehydecondensation product 3:2:l,

parts of kaolin,

22 parts of Champagne chalk;

b. parts of N-bicyclo[4.l.O]heptyl(7)-N',N-

dimethylurea,

5 parts of the sodium salt of oleylmethyl tauride,

2,5 parts of naphthalene sulfonic acid/formaldehyde condensationproduct,

0,5 part of carboxymethyl cellulose,

5 parts of neutral potassium aluminium silicate,

62 parts of kaolin;

c. 10 parts of N-bicyclo[4.l.0]heptyl(7)-N'-methyl- N-methoxy-urea,

3 parts of mixture of sodium alcohol sulfates,

5 parts of naphthalene sulfonic acid/formaldehyde condensation product,

82 parts of kaolin.

salts of saturated fatty responding carriers (kaolin and chalk) and thenmixed and ground. Wettable powders having excellent wettability andsuspensibility are obtained. By dilution with water, suspensions of anydesired concentration of the active ingredients can be obtained fromsuch wettable powders. Such suspensions are suitable for the control ofweeds and wild grasses in cultivated plantations.

EXAMPLE 9 The following ingredients are used for the preparation of a 45percent paste:

45 parts of N-bicyclo[3.l.0]hexyl(6)-N methylurea,

5 parts of sodium aluminium silicate,

14 parts of cetyl polyglycol ether with i 8 mol ethyleneoxide,

1 part of oleyl polyglycol ether with 5 mol ethyleneoxide,

2 parts of spindle oil,

10 parts of polyglycol (carbowax) 23 parts of water.

The active ingredient is intimately mixed and ground with the additivesin suitable apparatus. A paste is obtained which can be diluted withwater to prepare suspensions of any desired concentration. Thesesuspensions are suitable for the treatment of vegetable plantations.

EXAMPLE 10 To prepare a 10 emulsion concentrate l0 parts ofN-bicyclo[3.l.0]hexyl(6)-N'-methyl-N'- methoxy-urea, 15 parts of oleylpolyglycol ether having 5 mol of ethylene oxide, and parts of isphoroneare mixed together. This concentrate can be diluted with water toemulsions of suitable concentrations. Such emulsions are suitable forthe control of weeds in cultivated platations such as cotton, maize,etc.

We claim: 1. A composition comprising a herbicidally effective 'amountof a compound of the Formula I R1 0H, NH N\ wherein R represents amember selected from hydrogen,

lower alkyl and lower alkoxy,

R represents a member selected from lower alkyl,

lower alkenyl and lower alkynyl, and

n represents an integer of from 3 to 6, and an inert agriculturallyacceptable carrier and/or dispersing agent, compatible with saidcompound.

2. A composition as defined in claim 1, wherein said compound isN-bicyclo[4.Il;O]heptyl(7)-N,N'- dimethyl-urea.

3. A composition as defined in claim 1, wherein said compound isN-bicyclo[4.1.0]heptyl(7)-N'-methyl-N'- methoxy-urea.

4. A composition as defined in claim 1, wherein said compound isN-bicyclo[5. l .0]octyl( 8 )-N,N- dimethyl-urea.

Y 3,784,368 l5 l6 5. A composition as defined in claim 1, wherein saidwhich comprises applying to the locus of said weeds or compound isN-bicycl[6.l.0]nonyl(9)-N',N'- wild grasses a herbicidally effectiveamount of a comdimethyl-urea. pound as defined in claim 1.

6. A process for controlling weeds and wild grasses UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION Patent No. 317841368 Dated January 8,1974 Inv t r( Elmar Sturm and Christian Vogel It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Page one, first column, below the line reading [21] Appl. No. 285,364",insert the following:

- [30] Foreign Application Priority Data December 23, 1968 Switzerland19152/68 Signed and sealed this 1st day of April 1975.

SEAL) Attest:

C. FLARE-HALL DAY-TN '1 TH C. I LXSON Commissioner of Patents.--.ttesting Officer and Trademarks FORM PO-1050 (10-69) USCOMM-DC60876-3 69 u.s. covnnnnrr mun c-su

2. A composition as defined in claim 1, wherein said compound isN-bicyclo(4.1.0)heptyl(7)-N'',N''-dimethyl-urea.
 3. A composition asdefined in claim 1, wherein said compound isN-bicyclo(4.1.0)heptyl(7)-N''-methyl-N''-methoxy-urea.
 4. A compositionas defined in claim 1, wherein said compound isN-bicyclo(5.1.0)octyl(8)-N'',N''-dimethyl-urea.
 5. A composition asdefined in claim 1, wherein said compound isN-bicyclo(6.1.0)nonyl(9)-N'',N''-dimethyl-urea.
 6. A process forcontrolling weeds and wild grasses which comprises applying to the locusof said weeds or wild grasses a herbicidally effective amount of acompound as defined in claim